CN109592899B - Visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass with stable boron-oxygen network and preparation method thereof - Google Patents
Visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass with stable boron-oxygen network and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 144
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 77
- 239000004332 silver Substances 0.000 title claims abstract description 77
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 29
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims description 40
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 19
- 238000005286 illumination Methods 0.000 abstract description 11
- 238000001228 spectrum Methods 0.000 abstract description 11
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 15
- 238000002189 fluorescence spectrum Methods 0.000 description 15
- 239000004570 mortar (masonry) Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 229910052593 corundum Inorganic materials 0.000 description 9
- 239000010431 corundum Substances 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 9
- 230000005284 excitation Effects 0.000 description 9
- 238000000695 excitation spectrum Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- 239000000156 glass melt Substances 0.000 description 8
- 238000004847 absorption spectroscopy Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 238000001506 fluorescence spectroscopy Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 238000004611 spectroscopical analysis Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000013211 curve analysis Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/325—Fluoride glasses
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
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Abstract
The invention discloses visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass with a stable boron-oxygen network, which comprises the following components in percentage by mole: ZnF2(30—50％)、B2O3(30—50％)、SnO2(5—10％)、In2O3(5-10%) and Ag (1-30%). The invention adopts a two-step method of high-temperature melting. The glass prepared by the invention has the characteristic of adjustable visible light wave band and good physical and chemical stability, can be made into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or is matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Description
Technical Field
The invention relates to noble metal doped inorganic fluorescent glass and a preparation method thereof, in particular to visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass with stable boron-oxygen network and a preparation method thereof.
Background
Noble metal quantum clusters, in particular silver quantum clusters ([ Ag ]m]n+) The metal molecular luminescent material is a novel metal molecular luminescent material and has excellent optical, spectroscopic, catalytic and other properties. [ Ag ]m]n+The quantum cluster is composed of only a few to tens of atoms (Ag)0) Ion (Ag)+) The continuous energy level of the bulk metal material is split into discrete energy levels, strong quantum effect and molecular state fluorescence are generated, and the wide-spectrum adjustable fluorescence effect is achievedThe method has the advantage of high rate, so the method can be applied to the fields of biosensing, data storage, temperature detection, display, illumination and the like. Due to [ Ag ]m]n+The quantum cluster has high chemical activity, so the key point for obtaining the high-efficiency luminescent molecule lies in how to stabilize [ Agm]n+And (5) quantum clusters. Using organic polymers or proteins with [ Ag ]m]n+The formed complex structure can be effectively stabilized in inorganic glassm]n+Quantum clusters, but still suffer from poor thermal stability.
Disclosure of Invention
The invention aims to provide visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass with a stable boron-oxygen network and a preparation method thereof aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme: a visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass with stable boron-oxygen network comprises the following components in percentage by mole:
the invention also provides a preparation method of the visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass with stable boron-oxygen network, which comprises the following steps:
(1) respectively adopting ZnF2、H3BO3、SnO2、In2O3And AgNO3Introduction of powder raw material into ZnF2、B2O3、SnO2、In2O3And Ag, calculating the mass percent according to the composition measurement, and weighing the raw materials in proportion;
(2) ZnF is reacted with2、H3BO3And AgNO3Mixing raw material powder in an agate mortar uniformly, placing the mixture in a corundum crucible, melting the mixture for 0.5 to 1 hour at the temperature of 900-1200 ℃ in the air atmosphere, pouring the glass melt into a copper mold to be molded to obtain a glass block, and then crushing and grinding all glass samples prepared in the step into granules by using the agate mortarA powder having a degree of less than 50 microns;
(3) all the glass powder prepared in the step (2) and the SnO weighed in the step (1)2、In2O3Powder raw materials are evenly mixed in an agate mortar, placed in a corundum crucible, melted for 0.5 to 1 hour at the temperature of 1200 plus 1300 ℃ in the air atmosphere, and poured into a copper mold for molding to obtain a glass block;
(4) and (4) carrying out plane grinding and polishing on the glass prepared in the step (3) to prepare transparent glass.
The invention has the beneficial effects that: the visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass with stable boron-oxygen network has zinc-oxygen tetrahedron (ZnO)4]Boron-oxygen triangle (BO)3]And boron-oxygen tetrahedron [ BO4]Together as structural units forming a glass network, while the glass network outer body Sn4+、In3+、Zn2+And Ag+Can simultaneously adjust the charge balance of the glass network structure unit and the fluorescent silver quantum cluster [ Ag ] in the glassm]n+The role of redox balance. With substitution of Ag for B2O3The ratio is improved, the central wavelengths of the excitation spectrum and the emission spectrum are increased synchronously, the excitation wavelength is changed from about 340nm to about 430nm, the emission wavelength is changed from about 510nm to about 640nm, and the red shift characteristic is presented. Meanwhile, the fluorescent quantum efficiency of the fluorescent silver quantum cluster doped inorganic glass is stabilized between 77% and 92%, and the fluorescent silver quantum cluster doped inorganic glass has the advantage of high-efficiency luminescence. Therefore, the invention can design and regulate the fluorescent silver quantum cluster to realize the high-efficiency fluorescence emission of the target waveband in the ultra-wide waveband of the ultraviolet-visible light region by changing the silver content in the glass. All components of the glass are inorganic substances, so the glass has good physical and chemical stability and thermal stability, can be prepared into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Drawings
FIG. 1 shows a composition of 40ZnF of example 12-(50-x)B2O3-5SnO2-5In2O3-XRD pattern contrast of boron-oxygen network stable visible band tunable fluorescent silver quantum cluster doped inorganic glass with xAg (mol%, x ═ 1,4,7,10,13) with increasing Ag doping amount;
FIG. 2 shows a composition of 40ZnF in example 12-(50-x)B2O3-5SnO2-5In2O3A DTA curve comparison graph of the visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass with stable boron-oxygen network of xAg (mol%, x ═ 1,7,13) along with the increase of Ag doping amount;
FIG. 3 shows a composition of 40ZnF of example 12-46B2O3-5SnO2-5In2O34Ag (mol%) STEM-EDX scanning photo of visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass with stable boron-oxygen network;
FIG. 4 shows a composition of 40ZnF of example 12-(50-x)B2O3-5SnO2-5In2O3-xAg (mol%, x ═ 1,4,7,10,13) absorption spectrum contrast graph of visible band tunable fluorescent silver quantum cluster doped inorganic glass with stable boron-oxygen network as the Ag doping amount increases;
FIG. 5 shows a composition of 40ZnF of example 12-(50-x)B2O3-5SnO2-5In2O3A fluorescence spectrum contrast graph of the visible-band tunable fluorescent silver quantum cluster doped inorganic glass with stable boron-oxygen network of xAg (mol%, x ═ 1,4,7,10,13) along with the increase of the Ag doping amount; wherein the left side of the graph is the excitation spectrum and the right side is the emission spectrum. The central wavelength of the excitation peak is increased from 358nm to 418nm and the central wavelength of the emission peak is increased from 528nm to 615nm along with the increase of the doping amount of silver.
Detailed Description
In inorganic glass, silver exists in three forms, namely silver ions (Ag) in the order of size from small to large+) Silver quantum cluster ([ Ag ]m]n+) And silver nanoparticles. [ Ag ]m]n+With a certain charge, from a few to tens of atoms (Ag)0) Ion (Ag)+) Composition, low degree of polymerization, very small size (sub-nanometer scale). The silver nanoparticles are made of Ag0Atom composition, high polymerization degree and large size (nanometer level). The boron-oxygen network stable visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass needs to inhibit the formation of nano silver, mainly because the boron-oxygen network stable visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass has a strong Surface Plasmon Resonance (SPR) absorption effect in a visible waveband and does not generate any fluorescence emission. To produce [ Ag ] in large quantities in a glass matrixm]n+Requires Ag+Is partially reduced to Ag0At the same time, Ag should be inhibited+Is totally reduced to Ag0. Due to Ag+Is easier to be reduced into Ag in inorganic glass network0Therefore, in the present invention we introduce appropriate amount of Sn4+And In3+Partially stabilizing silver to Ag as an oxidizing agent+Simultaneous control of doped Ag concentration by solubility strategy [ Agm]n+M value of degree of polymerization of (1), using a zinc-oxygen tetrahedron [ ZnO ]4]Zinc oxygen octahedron [ ZnO ]8]Boron-oxygen trihedron [ BO3]And boron-oxygen tetrahedron [ BO4]Through [ Ag ]m]n+Strategies to promote [ Ag ] as charge compensatorsm]n+The aggregation value m of the polymer is increased, and the polymerization degree is improved.
The invention adopts non-bridge oxygen or non-charge balancing cation polyhedrons and [ Ag ] in inorganic glass networkm]n+The quantum clusters form similar complex structures, and can effectively stabilize [ Ag ]m]n+The quantum clusters can also improve the high-temperature stability and the size uniformity of the fluorescent material.
The glass has the characteristic of adjustable visible light wave band and good physical and chemical stability, can be made into a sheet and applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or is matched with an ultraviolet LED chip as a fluorescence conversion layer to be applied to white light LED illumination.
Example 1:
according to composition 40ZnF2-(50-x)B2O3-5SnO2-5In2O3-xAg (mol%, x ═ 1,4,7,10,13), the mass percentages of which are calculated and proportioned respectivelyWeighing ZnF2、H3BO3、SnO2、In2O3And AgNO3Powder raw material, ZnF is firstly put in an agate mortar2、H3BO3And AgNO3Mixing uniformly, placing the mixture in a corundum crucible, melting the mixture for 30 minutes at 900 ℃ in an air atmosphere, pouring the glass melt into a copper mold for molding to obtain a glass block, and then crushing and grinding the glass block into powder by using an agate mortar. Mixing the glass powder with the rest of the unused SnO2And In2O3After the powder raw materials are mixed, the mixture is melted in a glass melting furnace at the high temperature of 1200 ℃ for 30 minutes, then the crucible is taken out, the glass liquid is quickly poured into a copper mold for pressing and forming, and the glass is obtained after plane grinding and polishing.
The XRD analysis shown in figure 1 shows that all the glass samples in this series are amorphous. From the DTA curve analysis shown in FIG. 2, T of the series of samples was determinedg、TcThe content of the doped Ag is respectively reduced from 524.86 ℃ to 447.94 ℃ and from 624.28 ℃ to 543.34 ℃ along with the increase of the doped Ag content. The presence of silver quantum clusters in the glass was detected by scanning transmission electron microscopy-energy spectroscopy (STEM-EDX element surface scanning), absorption spectroscopy and fluorescence spectroscopy tests. As can be seen from the STEM-EDX scanning photographs of the glass shown in FIG. 3, a large number of sub-nanometer silver quantum clusters are uniformly distributed in the series of glasses. As can be seen from the absorption spectrum shown in FIG. 4, the absorption peak position of the central absorption wavelength of the fluorescent silver quantum clusters in the glass red shifts from 300nm to 420nm with the increase of the Ag incorporation amount. As seen from the fluorescence spectrum shown in FIG. 5, the central wavelength of the excitation spectrum was shifted from 358nm to 418nm in red, and the central wavelength of the emission spectrum was shifted from 528nm to 615nm in red. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the sample of the series is 88.26-91.23%, so that the visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass series with stable boron-oxygen network has high-efficiency fluorescence emission in an ultraviolet-visible light waveband, and the excitation wavelength and the emission wavelength are synchronously red-shifted along with the increase of the silver content. All the components of the silver quantum cluster doped inorganic glass series are inorganic substances, so that the silver quantum cluster doped inorganic glass series has good physical and chemical stability and thermal stability, and can be used for preparing a glass materialThe prepared slice is applied to modulating solar spectrum to improve the energy conversion efficiency of the solar cell, or is matched with an ultraviolet LED chip as a fluorescence conversion layer to be applied to white light LED illumination.
Example 2:
according to composition 30ZnF2-(60-x)B2O3-10SnO2-10In2O3-xAg (mol%, x ═ 22,24,26,28,30), calculating the mass percentage and weighing out the ZnF in proportion respectively2、H3BO3、SnO2、In2O3And AgNO3Powder raw material, ZnF is firstly put in an agate mortar2、H3BO3And AgNO3Mixing uniformly, placing the mixture in a corundum crucible, melting the mixture for 60 minutes at 1050 ℃ in air atmosphere, pouring the glass melt into a copper mold for molding to obtain a glass block, and then crushing and grinding the glass block into powder by using an agate mortar. Mixing the glass powder with the rest of the unused SnO2And In2O3After the powder raw materials are mixed, the mixture is melted for 45 minutes in a 1300 ℃ high-temperature glass melting furnace, the crucible is taken out, the glass liquid is quickly poured into a copper mold for pressing and forming, and the glass is prepared by plane grinding and polishing.
XRD analysis showed that all the glass samples in this series were amorphous. The T of the series of samples can be known from DTA curve test analysisg、TcThe content of the doped Ag is respectively reduced from 452.29 ℃ to 403.53 ℃ and from 529.92 ℃ to 454.87 ℃ along with the increase of the doped Ag content. The presence of silver quantum clusters in the glass was detected by scanning transmission electron microscopy-energy spectroscopy (STEM-EDX element surface scanning), absorption spectroscopy and fluorescence spectroscopy tests. As can be seen from the STEM-EDX scanning pictures of the glass, a large number of sub-nanometer silver quantum clusters are uniformly distributed in the series of glass. As can be seen from the absorption spectrum, the absorption peak position of the central absorption wavelength of the fluorescent silver quantum cluster in the glass is red-shifted from 410nm to 490nm along with the increase of the Ag doping amount. From the fluorescence spectrum, the central wavelength of the excitation spectrum was red shifted from 510nm to 622nm, and the central wavelength of the emission spectrum was red shifted from 347nm to 431 nm. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the samples of the series of the embodiment is 85.52-87.09%, so that the sample is preparedThe visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass series with stable boron-oxygen network provided by the embodiment of the invention has high-efficiency fluorescence emission in an ultraviolet-visible light waveband, and the excitation wavelength and the emission wavelength are synchronously red-shifted along with the increase of the silver content. All components of the silver quantum cluster doped inorganic glass series are inorganic substances, so that the silver quantum cluster doped inorganic glass series has good physical and chemical stability and thermal stability, can be prepared into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Example 3:
according to composition 30ZnF2-(55-x)B2O3-8SnO2-7In2O3-xAg (mol%, x ═ 7,9,11,13,15), calculating the mass percentage and weighing out the ZnF in proportion2、H3BO3、SnO2、In2O3And AgNO3Powder raw material, ZnF is firstly put in an agate mortar2、H3BO3And AgNO3Mixing evenly, placing the mixture in a corundum crucible, melting the mixture for 30 minutes at 1000 ℃ in air atmosphere, pouring the glass melt into a copper mold for molding to obtain a glass block, and then crushing and grinding the glass block into powder by using an agate mortar. Mixing the glass powder with the rest of the unused SnO2And In2O3After the powder raw materials are mixed, the mixture is melted for 45 minutes in a glass melting furnace with the high temperature of 1250 ℃, the crucible is taken out, the glass liquid is quickly poured into a copper mold for pressing and forming, and the glass is prepared by plane grinding and polishing.
XRD analysis showed that all the glass samples in this series were amorphous. The T of the series of samples can be known from the analysis of DTA curveg、TcThe content of the doped Ag is respectively reduced from 507.25 ℃ to 452.38 ℃ and from 594.88 ℃ to 556.29 ℃ along with the increase of the content of the doped Ag. The presence of silver quantum clusters in the glass was detected by scanning transmission electron microscopy-energy spectroscopy (STEM-EDX element surface scanning), absorption spectroscopy and fluorescence spectroscopy tests. As can be seen from the STEM-EDX scanning pictures of the glass, a large number of sub-nanometer silver quantum clusters are uniformly distributed in the series of glass. From the absorption spectrum, the glassThe position of the absorption peak of the central absorption wavelength of the fluorescent silver quantum cluster in the glass is red shifted from 360nm to 430nm along with the increase of the doping amount of Ag. From the fluorescence spectrum, the central wavelength of the excitation spectrum was red-shifted from 527nm to 581nm, and the central wavelength of the emission spectrum was red-shifted from 357nm to 399 nm. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the sample of the series is 82.37-84.27%, so that the visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass series with stable boron-oxygen network has high-efficiency fluorescence emission in an ultraviolet-visible light waveband, and the excitation wavelength and the emission wavelength are synchronously red-shifted along with the increase of the silver content. All components of the silver quantum cluster doped inorganic glass series are inorganic substances, so that the silver quantum cluster doped inorganic glass series has good physical and chemical stability and thermal stability, can be prepared into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Example 4:
according to composition 30ZnF2-(55-x)B2O3-10SnO2-5In2O3-xAg (mol%, x ═ 15,17,19,21,23), calculating the mass percentage and weighing out the ZnF in proportion2、H3BO3、SnO2、In2O3And AgNO3Powder raw material, ZnF is firstly put in an agate mortar2、H3BO3And AgNO3Mixing evenly, placing the mixture in a corundum crucible, melting the mixture for 30 minutes at 1000 ℃ in air atmosphere, pouring the glass melt into a copper mold for molding to obtain a glass block, and then crushing and grinding the glass block into powder by using an agate mortar. Mixing the glass powder with the rest of the unused SnO2And In2O3After the powder raw materials are mixed, the mixture is melted in a glass melting furnace with the high temperature of 1250 ℃ for 60 minutes, the crucible is taken out, the glass liquid is quickly poured into a copper mold for pressing and forming, and the glass is obtained after plane grinding and polishing.
XRD analysis showed that all the glass samples in this series were amorphous. The T of the series of samples can be known from the analysis of DTA curveg、TcWith the incorporation ofThe increase in Ag content was reduced from 463.88 ℃ to 407.96 ℃ and from 564.01 ℃ to 502.67 ℃, respectively. The presence of silver quantum clusters in the glass was detected by scanning transmission electron microscopy-energy spectroscopy (STEM-EDX element surface scanning), absorption spectroscopy and fluorescence spectroscopy tests. As can be seen from the STEM-EDX scanning pictures of the glass, a large number of sub-nanometer silver quantum clusters are uniformly distributed in the series of glass. As can be seen from the absorption spectrum, the absorption peak position of the central absorption wavelength of the fluorescent silver quantum cluster in the glass is red-shifted from 410nm to 470nm along with the increase of the Ag doping amount. From the fluorescence spectrum, the central wavelength of the excitation spectrum was red-shifted from 584nm to 639nm, and the central wavelength of the emission spectrum was red-shifted from 395nm to 421 nm. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the sample of the series is 81.65-83.44%, so that the visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass series with stable boron-oxygen network has high-efficiency fluorescence emission in an ultraviolet-visible light waveband, and the excitation wavelength and the emission wavelength are synchronously red-shifted along with the increase of the silver content. All components of the silver quantum cluster doped inorganic glass series are inorganic substances, so that the silver quantum cluster doped inorganic glass series has good physical and chemical stability and thermal stability, can be prepared into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Example 5:
according to composition 35ZnF2-(45-x)B2O3-10SnO2-10In2O3-xAg (mol%, x ═ 4,7,10,13,16), calculating the mass percentage and weighing out the ZnF in proportion2、H3BO3、SnO2、In2O3And AgNO3Powder raw material, ZnF is firstly put in an agate mortar2、H3BO3And AgNO3Mixing uniformly, placing the mixture in a corundum crucible, melting the mixture for 60 minutes at 1150 ℃ in an air atmosphere, pouring the glass melt into a copper mold for molding to obtain a glass block, and then crushing and grinding the glass block into powder by using an agate mortar. Mixing the glass powder with the rest of the unused SnO2And In2O3Powder ofAfter the raw materials are mixed and melted in a glass melting furnace at the high temperature of 1300 ℃ for 60 minutes, the crucible is taken out, the glass liquid is quickly poured into a copper mold for pressing and forming, and the glass is obtained after plane grinding and polishing.
XRD analysis showed that all the glass samples in this series were amorphous. The T of the series of samples can be known from the analysis of DTA curveg、TcThe content of the doped Ag is respectively reduced from 509.87 ℃ to 429.55 ℃ and from 598.26 ℃ to 547.47 ℃. The presence of silver quantum clusters in the glass was detected by scanning transmission electron microscopy-energy spectroscopy (STEM-EDX element surface scanning), absorption spectroscopy and fluorescence spectroscopy tests. As can be seen from the STEM-EDX scanning pictures of the glass, a large number of sub-nanometer silver quantum clusters are uniformly distributed in the series of glass. As can be seen from the absorption spectrum, the absorption peak position of the central absorption wavelength of the fluorescent silver quantum cluster in the glass is red shifted from 320nm to 390nm along with the increase of the Ag doping amount. From the fluorescence spectrum, the center wavelength of the excitation spectrum was red-shifted from 509nm to 595nm, and the center wavelength of the emission spectrum was red-shifted from 346nm to 388 nm. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the sample of the series is 83.64-87.29%, so that the visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass series with stable boron-oxygen network has high-efficiency fluorescence emission in an ultraviolet-visible light waveband, and the excitation wavelength and the emission wavelength are synchronously red-shifted along with the increase of the silver content. All components of the silver quantum cluster doped inorganic glass series are inorganic substances, so that the silver quantum cluster doped inorganic glass series has good physical and chemical stability and thermal stability, can be prepared into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Example 6:
according to composition 50ZnF2-(35-x)B2O3-6SnO2-9In2O3-xAg (mol%, x ═ 1,3,5,7,9), calculating the mass percentage and weighing out the ZnF in proportion2、H3BO3、SnO2、In2O3And AgNO3Raw materials of powder in an agate mortarFirstly ZnF2、H3BO3And AgNO3Mixing evenly, placing the mixture in a corundum crucible, melting the mixture for 30 minutes at 1000 ℃ in air atmosphere, pouring the glass melt into a copper mold for molding to obtain a glass block, and then crushing and grinding the glass block into powder by using an agate mortar. Mixing the glass powder with the rest of the unused SnO2And In2O3After the powder raw materials are mixed, the mixture is melted for 45 minutes in a glass melting furnace with the high temperature of 1250 ℃, the crucible is taken out, the glass liquid is quickly poured into a copper mold for pressing and forming, and the glass is prepared by plane grinding and polishing.
XRD analysis showed that all the glass samples in this series were amorphous. The T of the series of samples can be known from the analysis of DTA curveg、TcThe content of the doped Ag is respectively reduced from 519.29 ℃ to 470.21 ℃ and from 609.00 ℃ to 557.84 ℃ along with the increase of the doped Ag content. The presence of silver quantum clusters in the glass was detected by scanning transmission electron microscopy-energy spectroscopy (STEM-EDX element surface scanning), absorption spectroscopy and fluorescence spectroscopy tests. As can be seen from the STEM-EDX scanning pictures of the glass, a large number of sub-nanometer silver quantum clusters are uniformly distributed in the series of glass. As can be seen from the absorption spectrum, the absorption peak position of the central absorption wavelength of the fluorescent silver quantum cluster in the glass is red-shifted from 310nm to 350nm along with the increase of the doping amount of Ag. From the fluorescence spectrum, the central wavelength of the excitation spectrum was red shifted from 534nm to 611nm, and the central wavelength of the emission spectrum was red shifted from 352nm to 401 nm. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the sample of the series is 78.53-83.49%, so that the visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass series with stable boron-oxygen network has high-efficiency fluorescence emission in an ultraviolet-visible light waveband, and the excitation wavelength and the emission wavelength are synchronously red-shifted along with the increase of the silver content. All components of the silver quantum cluster doped inorganic glass series are inorganic substances, so that the silver quantum cluster doped inorganic glass series has good physical and chemical stability and thermal stability, can be prepared into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Example 7:
according to composition 35ZnF2-(50-x)B2O3-7SnO2-8In2O3-xAg (mol%, x ═ 1,5,9,13,17), calculating the mass percentage and weighing out the ZnF in proportion2、H3BO3、SnO2、In2O3And AgNO3Powder raw material, ZnF is firstly put in an agate mortar2、H3BO3And AgNO3Mixing uniformly, placing the mixture into a corundum crucible, melting the mixture for 45 minutes at 1250 ℃ in air atmosphere, pouring the glass melt into a copper mold for molding to obtain a glass block, and then crushing and grinding the glass block into powder by using an agate mortar. Mixing the glass powder with the rest of the unused SnO2And In2O3After the powder raw materials are mixed, the mixture is melted in a glass melting furnace at the high temperature of 1300 ℃ for 60 minutes, the crucible is taken out, the glass liquid is quickly poured into a copper mold for pressing and forming, and the glass is obtained after plane grinding and polishing.
XRD analysis showed that all the glass samples in this series were amorphous. The T of the series of samples can be known from the analysis of DTA curveg、TcThe content of the doped Ag is respectively reduced from 538.58 ℃ to 424.65 ℃ and from 617.06 ℃ to 533.85 ℃ along with the increase of the doped Ag content. The presence of silver quantum clusters in the glass was detected by scanning transmission electron microscopy-energy spectroscopy (STEM-EDX element surface scanning), absorption spectroscopy and fluorescence spectroscopy tests. As can be seen from the STEM-EDX scanning pictures of the glass, a large number of sub-nanometer silver quantum clusters are uniformly distributed in the series of glass. As can be seen from the absorption spectrum, the absorption peak position of the central absorption wavelength of the fluorescent silver quantum cluster in the glass is red shifted from 320nm to 430nm along with the increase of the Ag doping amount. From the fluorescence spectrum, the center wavelength of the excitation spectrum was shifted from 531nm to 627nm in red, and the center wavelength of the emission spectrum was shifted from 361nm to 427nm in red. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the samples of the series is 87.00-91.52%, so that the visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass series with stable boron-oxygen network has high-efficiency fluorescence emission in an ultraviolet-visible light waveband, and the excitation wavelength and the emission wavelength are increased along with the increase of the silver contentAnd synchronously red-shifting. All components of the silver quantum cluster doped inorganic glass series are inorganic substances, so that the silver quantum cluster doped inorganic glass series has good physical and chemical stability and thermal stability, can be prepared into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the appended claims.
Claims (2)
1. The visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass with stable boron-oxygen network is characterized by comprising the following components in percentage by mol:
2. the preparation method of the visible waveband adjustable fluorescent silver quantum cluster doped inorganic glass with stable boron-oxygen network according to claim 1 is characterized by comprising the following steps:
(1) ZnF is reacted with2、H3BO3、SnO2、In2O3And AgNO3Taking the powder raw materials according to the mol percentage;
(2) ZnF is reacted with2、H3BO3And AgNO3Uniformly mixing powder raw materials, melting at 900-1200 ℃ for 0.5-1 hour in an air atmosphere, pouring into a mold for molding to obtain a glass block, and then crushing and grinding the glass block into powder;
(3) mixing the powder prepared in the step 2 and the SnO weighed in the step 12、In2O3Uniformly mixing the powder raw materials, melting the powder raw materials for 0.5 to 1 hour at 1200 to 1300 ℃ in an air atmosphere, and pouring the melted powder into a mold for molding to obtain a glass block;
(4) and (4) carrying out plane grinding and polishing on the glass block material prepared in the step (3) to prepare transparent glass.
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